Microcapsule and method of producing same

ABSTRACT

A microcapsule which is able to stably retain a benefit agent such as a volatile substance for an extended period, and which is also suitable for encapsulating fragrances and the like. Such capsule encapsulates a mixture comprising a volatile substance, and an additive that has a higher melting point than the volatile substance and is able to undergo mutual dissolution with the volatile substance, wherein the mixture exhibits a melting point range, and a portion of, or all of, that melting point range falls within a range from −20 to 60° C. The present invention also relates to consumer products including cleaning and/or treatment compositions comprising such microcapsules, and processes of making and using same.

RELATED APPLICATION

The present application claims priority under 35 U.S.C. §119 of U.S.Application Ser. No. 60/720,861 filed Sep. 27, 2005.

FIELD OF THE INVENTION

The present invention relates to a microcapsule that encapsulates avolatile substance such as a fragrance, and a method of producing such amicrocapsule. The present invention also relates to consumer productscomprising such microcapsules, and processes of making and using same.

BACKGROUND OF THE INVENTION

Various benefit agents, such fragrances, are expensive and/or difficultto deliver as neat liquids as they exhibit high volatility, and rapidlylose their aroma if left exposed to the atmosphere. As a result,fragrances have been microcapsulated. That is, sealed inside a capsule,to enable the aroma to be retained. However, even if a benefit agentsuch as a highly volatile fragrance is sealed within a microcapsule, thefragrance still can escape through gaps within the microcapsules cellwall. Thus, long term storage, particularly in the presence of othermaterials, is a problem. A technique described in Japanese Laid-OpenPublication No. Hei 9-911, wherein a volatile substance is encapsulatedby incorporation within a gel-like polyurethane resin, attempts to solvethis problem. In this technique, during the capsulation process, apolyfunctional isocyanate and a polyol are reacted together to produce agel-like polyurethane resin, and the volatile substance is incorporatedwithin this polyurethane resin. Thus, while not being bound by theory,it is believed that release of the volatile substance from the capsulecore is suppressed. Unfortunately such technique employs isocyanatewhich can produce an irritating odor that detracts from benefit agents,particularly the aroma of the fragrance. In addition, improvement isalso desirable in terms of the fact that the proportion of thepolyurethane resin in the encapsulated material at the core is quitehigh relative to the quantity of the target volatile substance. Such animproved microcapsule is particularly desirable as consumers typicallyassociate the odor of a cleaned or treated article with the degree ofcleanliness or freshness of such article.

Accordingly, the present invention provides a microcapsule which is ableto stably retain a volatile substance for an extended period, in thepresence of other materials, such as consumer product formulations. Suchmicrocapsule is particularly suitable for encapsulating fragrances andthe like. In addition, consumer products, including cleaning and/ortreatment compositions that contain the aforementioned microcapsules andprocesses of making and using same are disclosed

SUMMARY OF THE INVENTION

The present invention relates to a microcapsule which encapsulates amixture comprising a volatile substance, and an additive that has ahigher melting point than the volatile substance and is able to undergomutual dissolution with the volatile substance, wherein the mixtureexhibits a melting point range, and a portion of, or all of, the meltingpoint range falls within a range from −20 to 60° C.

Another aspect of the present invention relates to a method of producingthe microcapsule according to the above aspect of the present invention,comprising: preparing an emulsion of the mixture comprising the volatilesubstance, and the additive that has a higher melting point than thevolatile substance and is able to undergo mutual dissolution with thevolatile substance; and adding a membrane material to the emulsion andconducting a polymerization, thereby forming a microcapsule whichencapsulates the mixture.

The present invention also relates to consumer products includingcleaning and/or treatment compositions comprising such microcapsules,and processes of making and using same.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein consumer products include articles and cleaning andtreatment compositions.

As used herein, the term “cleaning and/or treatment composition”includes, unless otherwise indicated, granular or powder-formall-purpose or “heavy-duty” washing agents, especially laundrydetergents; liquid, gel or paste-form all-purpose washing agents,especially the so-called heavy-duty liquid types; liquid fine-fabricdetergents; hand dishwashing agents or light duty dishwashing agents,especially those of the high-foaming type; machine dishwashing agents,including the various tablet, granular, liquid and rinse-aid types forhousehold and institutional use; liquid cleaning and disinfectingagents, including antibacterial hand-wash types, laundry bars,mouthwashes, denture cleaners, car or carpet shampoos, bathroomcleaners; hair shampoos and hair-rinses; shower gels and foam baths andmetal cleaners; as well as cleaning auxiliaries such as bleach additivesand “stain-stick” or pre-treat types.

As used herein, the phrase “is independently selected from the groupconsisting of . . . ” means that moieties or elements that are selectedfrom the referenced Markush group can be the same, can be different orany mixture of elements.

As used herein, the articles “a” and “an” when used in the specificationor a claim, are understood to mean one or more of what is claimed ordescribed.

The test methods disclosed in the Test Methods Section of the presentapplication must be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active level of that component or composition, and areexclusive of impurities, for example, residual solvents or by-products,which may be present in commercially available sources.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

Microcapsules

In a volatile substance encapsulated microcapsule according to thepresent invention, a mixture is formed at the core in which the additivethat has a higher melting point than the volatile substance is mutuallydissolved with the volatile substance. By forming a mixture of thevolatile substance and the additive in this manner, the melting point,boiling point, and volatilization temperature of the volatile substanceare adjusted, enabling the volatility of the volatile substance to besuppressed to low levels.

As a result, release of the volatile substance inside the microcapsuleis suppressed, enabling stable retention and sustained release of thevolatile substance over an extended period.

In addition, because the range of possible additives is broad, anadditive can be selected in accordance with the properties of thevolatile substance. For example, an odorless additive can be selected inthe case of a fragrance, meaning it is possible to form a huge varietyof encapsulated substances.

A microcapsule according to the present invention (hereafter alsoreferred to as simply a “capsule”) encapsulates a mixture (hereafteralso referred to as the “encapsulated material” or “encapsulationmaterial”) comprising a volatile substance, and an additive that has ahigher melting point than the volatile substance and is able to undergomutual dissolution with the volatile substance.

Because the volatile substance and the additive are able to undergomutual dissolution, the mixture exists as a homogenous substance of thetwo substances. This mixture exhibits a melting point range (T1−T2,wherein T1<T2), and either a portion of, or all of, this melting pointrange falls within a range from −20 to 60° C. This includes those caseswhere at least one, or perhaps both, of the lower limit temperature T1and the upper limit temperature T2 of this melting point range fallwithin the range from −20 to 60° C., and those cases where the meltingpoint range T1−T2 is broader than the range from −20 to 60° C., andincludes the entire range from −20 to 60° C.

In other words, the possible cases include (1) T1<−20° C.<T2<60° C.(wherein only T2 falls within the specified range), (2) −20°C.≦T1<T2≦60° C. (wherein both T1 and T2 fall within the specifiedrange), (3) −20° C.<T1<60° C.<T2 (wherein only T1 falls within thespecified range, and (4) T1<−20° C. and 60° C.<T2 (wherein T1−T2includes the entire specified range from −20 to 60° C.).

Including the melting point (T3) of the volatile substance, and themelting point (T4, wherein T3<T4) of the additive, yields therelationship T3<T1<T2<T4.

Within this melting point range (T1−T2), the mixture adopts a state inwhich solid and liquid coexist. In this description, this state isreferred to as a “semisolid” state. In other words, the melting pointrange described above is the temperature range over which the mixtureexists as a semisolid.

At temperatures higher than T2, (a) the mixture is a homogenous solution(liquid). When the temperature is lowered gradually to less than T2, (b)a solid starts to gradually precipitate out of the solution, producing asemisolid state. As the temperature is lowered further, (c) the solidportion gradually increases, (d) the fluidity falls, producing asorbet-like state, and then (e) the entire mixture develops rigidity.Finally, when the temperature falls below T1, (f) the mixture becomescompletely solid. By gradually lowering the temperature in this manner,the state of the mixture can be changed (a)→(b)→(c)→(d)→(e)→(f), and theterm “semisolid” refers to all of these states except for (a) and (f).

T2 refers to the temperature at which solid material, no matter howsmall, starts to become visible within the liquid (the temperature atwhich visual inspection no longer reveals a liquid free of solids). T1refers to the temperature at which fluidity disappears (or thetemperature at which fluidity commences). The existence or absence offluidity is determined by bringing a cylindrical glass rod with across-sectional diameter of 7 mm (wherein the tip of the rod has beencut through the cross section to generate a flat end face) intoperpendicular contact with the surface of a mixture inside a container(a 100 ml beaker), applying a load of 700 gf, and observing whether ornot the tip of the glass rod penetrates into the mixture. Accordingly,T1 refers to the temperature at which the glass rod is no longer able topenetrate (or the temperature at which the rod is first able topenetrate) the mixture.

The measurements of T2 and T1 are conducted by first converting themixture to a liquid, and then observing the changes in state as thetemperature is gradually lowered.

Although the solid that first begins to precipitate as the temperatureis gradually lowered comprises predominantly the higher melting pointcomponent, namely the additive, it is thought that the solid alsoincorporates a portion of the volatile substance. It is thought that asthe temperature is lowered, the proportion of the volatile substancewithin the solid increases. In contrast, although the liquid phasewithin the semisolid comprises mostly the volatile substance, it isthought that the liquid also incorporates a portion of the additive. Inother words, although the proportions of the solid component and theliquid component within the semisolid, and the respective compositionsof the two components vary depending on the temperature, it is believedthat the fact that the solid component and the liquid component co-existwithin the melting point range enables the stability of the volatilesubstance to be improve.

The melting point range for pure substances is usually quite narrow,whereas the melting point range for mixtures is often much broader. Inthe case of mixtures of substances with a large difference in meltingpoints, even wider melting point ranges can be obtained.

In the present invention, the volatile substance itself is often amixture of organic compounds with different melting points, and additionof the additive produces a mixture of even more compounds, meaning amixture with a broader melting point range is obtained.

The broadening of the melting point range for the mixture in this manneris advantageous in the present invention. In the semisolid state, anequilibrium is maintained between volatilization and retention of thevolatile substance, enabling both volatilization and retention to beachieved in a favorable balance.

In order to suppress the volatility of the volatile substance, either aportion of, or all of, the melting point range for the mixture must fallwithin a range from −20 to 60° C., and preferably falls within a rangefrom −10 to 55° C. In addition, cases in which either a portion of, orall of, the melting point range for the mixture falls within a rangefrom 0 to 50° C., which represents the temperature band in which normalhuman life is conducted, is even more desirable. The reason for thisdesirability is that if the upper limit temperature T2 for the semisolidstate is lower than 0° C., then the encapsulated material comprising thevolatile substance will be liquid under normal usage conditions,increasing the danger that the volatility will be unable to beadequately suppressed, whereas in contrast, if the lower limittemperature T1 for the semisolid state exceeds 50° C., then theencapsulated material comprising the volatile substance will becompletely solid under normal usage conditions, increasing the dangerthat the volatility will be overly suppressed, meaning the effect of thevolatile substance will not manifest adequately.

Furthermore, if the upper limit temperature T2 for the melting pointrange is 60° C. or lower, so that the mixture is liquid at temperaturesexceeding 60° C., then a further benefit is obtained in that when an insitu polymerization method is selected as the microcapsulation methoddescribed below, the capsulation can be completed easily at atemperature of 60 to 80° C.

In other words, cases in which the melting point range satisfies either(1) T1<−20° C.<T2<60° C., or (2) −20° C.≦T1<T2≦60° C. are preferred.Alternatively, T2 is preferably within a range from 40 to 60° C., andeven more preferably from 40 to 55° C., and most preferably from 40 to50° C.

On the other hand, the lower limit temperature T1 for the melting pointrange is preferably 30° C. or lower, and even more preferably 20° C. orlower, and most preferably 10° C. or lower. Although there are noparticular lower limits for T1, considering normal usage conditions andthe need to achieve the required melting point range, T1 values of atleast −10° C. suffice, and values of −20° C. or greater are quitesatisfactory.

In addition, the difference between T1 and T2 (the melting point range)is preferably at least approximately 10° C., and preferably at leastapproximately 20° C., even more preferably at least approximately 30°C., even more preferably at least approximately 40° C., and is mostpreferably 50° C. or greater.

In the present invention, in addition to the sustained release effectobtained as a result of the microcapsulation, the fact that theencapsulated material is in a semisolid state enables the storagestability and sustained releasability of the volatile substance to beimproved dramatically.

Furthermore, because the encapsulated material is a semisolid, themembrane strength relative to external pressure can be increasedcompared with the case of a liquid material. As a result, a capsule ofadequate strength can be formed even if the proportion of the capsuleaccounted for by the membrane material (the cell material or the wallmaterial) is reduced, and the proportion of the encapsulated material isincreased.

Generally when microcapsules are dispersed within a liquid solvent suchas a liquid ink, a liquid cosmetic, or a liquid cleaning agent or thelike, there is a danger that solvent passing through the capsulemembrane and penetrating the capsule interior may cause a deteriorationin the stability of the volatile substance. Moreover, in those caseswhere the encapsulated material is a liquid, the encapsulated materialis prone to passing through the capsule membrane and being eluted intothe external phase.

In contrast, in the present invention, the volatile substance isincorporated within a semisolid-state mixture, meaning the properties ofthe volatile substance can be stably maintained, even under this type ofattack by an external solvent, and elution of the encapsulated materialinto the external phase can be prevented, thus providing improvedstability relative to the capsule external phase.

In addition, because a portion of the high-cost volatile substance canbe replaced with a comparatively low-cost additive within theencapsulated material, the present invention is also advantageous from acost perspective.

Examples of suitable volatile substances include a variety of reagents(active ingredients) that exhibit volatility, including the variousfragrances, plant-based essential oils, deodorants, deodorizers,repellents, insect repellents, insecticides, and agricultural chemicals,and the present invention is suited to any of these materials when it isimportant to enable the effect of the active ingredient to manifest overan extended period. Combinations of two or more of these volatilesubstances may also be used.

Specific examples of suitable fragrances include animal and plant-bawdnatural fragrances such as musk, civet, castorium, rose, jasmine,orange, lavender, sandalwood, cinnamon, rosemary, lemon, iris, violet,lily of the valley, lily, lime, vanilla, and mint; synthetic versions ofthese natural fragrances; and synthetic fragrances such as lilac,carnation, cosmos, amaryllis, fragrant olive, tulip, sweet briar, rugosarose, sasanqua, thistle, camellia, sage, hyacinth, chrysanthemum, cedar,bouquet, citron, kabosu, coffee, curry, garlic, matsutake mushroom,banana, chocolate, yoghurt, watermelon, beef, sauce, and steak.

Of these, oily fragrances are preferred, and fragrances such as orange,grape, grapefruit, apple, strawberry, pineapple, peach, melon, lime,blueberry, lemon, mint, lavender, eucalyptus, rose, rosemary, lily ofthe valley, lily, freesia, cypress, and white cedar are particularlypreferred.

Examples of suitable plant-based essential oils (natural essential oils)include eucalyptus, orange, lavender, lemon, lemongrass, peppermint, teatree, rosewood, citronella, rosemary, ylang-ylang, bergamot, marjoram,myrtle, chamomile, neroli, jasmine, cinnamon, ginger, thyme, palmarosa,fennel, lime, basil, patchouli, black pepper, and rose absolute.

Examples of suitable repellents and insect repellents include capsaicin,peppermint oil, eucalyptus, cypress, white cedar, menthol oil, allylisothiocyanate, methyl salicylate, ethyl salicylate, and nonylic acidvanillylamide.

Examples of suitable deodorants and deodorizers include phthalateesters, phosphate esters, plant-based oil extracts, and terpene-baseddeodorizers.

Examples of suitable agricultural chemicals include fenitrothion, methylparathion, parathion, diazinon, warfarin, alachlor, pyrethrin,cycloheximide, sethoxydim, and triflumizole.

Examples of suitable insecticides include permethrin, pyrethroidcompounds, and fipronil.

There are no particular restrictions on the additive, provided it has amelting point T4 that is higher than the melting point T3 of thevolatile substance (namely, T3<T4), is able to undergo mutualdissolution with the encapsulated volatile substance, and ondissolution, is able to form a mixture with a melting point that fallswithin a range from −20 to 60′C.

For example, provided the additive is a compound with a melting point T4that falls within a range from 25 to 200° C., preparing a mixture withthe volatile substance for which either a portion of, or all of, themelting point range (T1−T2) falls within the above range iscomparatively simple, and consequently such additives are preferred. Ifthe additive has a melting point higher than 200° C., then dissolutionwith the volatile substance may become difficult, depending on thenature of the volatile substance.

In accordance with the usage conditions for the microcapsules, compoundswith a melting point T4 that falls within a range from 40 to 120° C., oreven more preferably from 50 to 100° C., are particularly desirable.

In terms of the general properties of the additive, the additive itselfpreferably has either no odor or very little odor, so that in thosecases where a fragrance is encapsulated as the volatile substance, theadditive does not impair the characteristics of the fragrance. Inaddition, the use of compounds that are stable under heat and light isalso preferred.

From the viewpoints of workability during microcapsulation andsolubility in the volatile substance, generally, the additive ispreferably a lipophilic compound (with low solubility in water).

Specifically, compounds that contain a hydroxyl group and/or a carboxylgroup are preferred, and the use of alcohols, carboxylic acids, orhydroxy acids with melting points within the range from 25 to 200° C. isparticularly desirable. Alternatively, the use of paraffin (paraffinhydrocarbons) is also desirable. In addition to these compounds, polymercompounds (such as plastics and unvulcanized rubber) that are capable ofdissolution in the volatile substance can also be used.

These additives can be used either alone, or in combinations of two ormore different compounds.

Specific examples of suitable alcohols include straight-chain orbranched-chain higher aliphatic alcohols with 12 or more carbon atoms,such as lauryl alcohol, myristyl alcohol, palmityl alcohol, cetylalcohol, stearyl alcohol, 2-octyldodecanol, and behenyl alcohol. Mixedalcohols produced by mixing two or more of these alcohols can also beused.

Alternatively, mixtures of one or more of these alcohols of 12 or morecarbon atoms and one or more aliphatic alcohols with less than 12 carbonatoms can also be used favorably.

In addition, the aliphatic alcohol may also be a derivative of asulfonic acid or phosphoric acid, or a derivative that contains ahalogen, nitrogen, sulfur, or phosphorus or the like.

Both aliphatic carboxylic acids and aromatic carboxylic acids can beused as the carboxylic acid, and specific examples of suitable acidsinclude lauric acid, myristic acid, palmitic acid, behenic acid, stearicacid, arachidic acid, ligonceric acid, crotonic acid, elaidic acid,erucic acid, nervonic acid, benzoic acid, and methylbenzoic acid.

An example of a suitable hydroxy acid is salicylic acid.

Suitable paraffin compounds include mixtures containing hydrocarbonswith 20 or more carbon atoms. These mixtures may also includehydrocarbons with less than 20 carbon atoms.

There are no particular restrictions on the ratio between the volatilesubstance and the additive within the mixture, and this ratio ispreferably adjusted in accordance with the melting points of the twomaterials. For example, in those cases where the melting point of theadditive is relatively high in relation to the melting point and boilingpoint of the volatile substance (or those cases where the melting pointand boiling point of the volatile substance is relatively low inrelation to the melting point of the additive; in other words, thosecases where T4−T3 is large), the blend quantity of the additive requiredto ensure that the melting point of the mixture falls within thespecified temperature range is comparatively small. In contrast, inthose cases where the melting point of the additive is relatively low inrelation to the melting point and boiling point of the volatilesubstance (or those cases where the melting point and boiling point ofthe volatile substance is relatively high in relation to the meltingpoint of the additive; in other words, those cases where T4−T3 issmall), the additive must be added in a much larger quantity.

Specifically, the blend quantity of the additive is preferably within arange from 10 to 200 parts by weight, and even more preferably from 10to 100 parts by weight, and most preferably from 20 to 50 parts byweight, per 100 parts by weight of the volatile substance. Particularlyin those cases where the volatile substance is a fragrance, in order toensure adequate manifestation of the aroma, the blend quantity of theadditive is preferably no more than 100 parts by weight, that is, withina range from 10 to 100 parts by weight, and is even more preferably from20 to 50 parts by weight, per 100 parts by weight of the fragrance.

More specifically, the addition of 20 to 50 parts by weight of anadditive with a melting point from 50 to 100° C. to 100 parts by weightof the volatile substance, thereby producing a mixture with a meltingpoint that falls within a range from 0 to 50° C. is extremely desirable.This ability to increase the relative blend quantity of the volatilesubstance within the mixture of a preferred embodiment is one of thecharacteristic features of the present invention. In such cases, theadditive is dissolved in the volatile substance.

The mixture that constitutes the encapsulated material of themicrocapsule may also comprise other components in addition to thevolatile substance and the additive. Examples of these other componentsinclude organic solvents such as toluene, xylene, and hexane, as well aslubricants, dyes, organic and inorganic pigments, antioxidants,ultraviolet absorbers, and other organic compounds.

There are no particular restrictions on the membrane material of themicrocapsule, and suitable examples include organic polymer materialssuch as gelatin, gelatin-gum Arabic, acrylic resins, urethane resins,melamine resins, urea-formalin resins, nylons, polyethers, alginic acid,polyvinyl alcohol, polystyrene, paraffin, and cellulose; and inorganicmaterials such as titanium dioxide, calcium carbonate, carbon black,silica, alkali earth metals, silicates, iron oxides, cobalt carbonate,and zinc oxide.

Processes of Making Microcapsules

Microcapsulation of the encapsulation material can be conducted using avariety of methods, including interfacial polymerization, in situpolymerization, coacervation, in-liquid drying, spray drying, in-liquidcuring, and air suspension. Of these methods, interfacialpolymerization, in situ polymerization, and coacervation are preferred,and in situ polymerization methods are particularly desirable.

In those cases where the encapsulation material is oily (an oil phase),the microcapsule may be prepared in an aqueous system.

For example, in situ polymerization includes: preparing an emulsion of amixture comprising the volatile substance, and the additive that has ahigher melting point than the volatile substance and is able to undergomutual dissolution with the volatile substance; and adding a membranematerial to the emulsion and conducting a polymerization, therebyforming a microcapsule which encapsulates the mixture. By using thisproduction method, a microcapsule according to the present invention canbe favorably produced.

As follows is a description of a preferred embodiment of the presentinvention.

First, a volatile substance such as an oily fragrance, and an additiveare mixed together at a temperature exceeding the melting point T4 ofthe additive, thus yielding a mixture in which the two materials aremutually dissolved. A pH regulator is preferably used to adjust pH ofthe mixture. Examples of acids as the pH regulator include formic acid,acetic acid, citric acid, hydrochloric acid, sulfuric acid, phosphoricacid, nitric acid, tartaric acid, boric acid, and fumaric acid. Examplesof alkalis include alkali metal hydroxides, ammonia, andtriethanolamine.

While still in a liquid state, this (lipophilic) mixture is then mixedwith water, and emulsified, thus preparing an emulsion. During thisstep, an emulsion accelerator or the like is preferably used tostabilize the oil droplets of the mixture. An anionic water-solublepolymer is preferably used as the emulsion accelerator formicrocapsulation. Examples of anionic water-soluble polymers includeethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer,methylvinyl ether-maleic anhydride copolymer, polyacrylic acid,polystyrenesulfonic acid, acrylic acid-styrenesulfonic acid copolymer,acrylic acid-acrylamide-acrylonitrile ternary copolymer, and acrylicacid-acrylonitrile-acid phosphoxy polyethyleneglycol methacrylateternary copolymer.

Subsequently, a membrane material (such as a prepolymer) is added tothis emulsion, and this membrane material is then polymerized around theperiphery of the oil droplets, thus forming the microcapsule walls. Thisyields a microcapsule slurry. If necessary, the solvent can be removedfrom the slurry to produce a microcapsule powder.

Emulsification of the mixture can be conducted using a typicalemulsification-dispersion device such as a stirrer, homomixer,homodisper, homojetter, colloid mill, ultrasonic dispersion device, orultrasonic emulsifier. Specific examples of suitable commerciallyavailable devices include general stirrers such as the BL-series 3-1motor stirrers (manufactured by Shinto Scientific Co., Ltd.) and theA520 portable mixer (manufactured by Satake Chemical Equipment Mfg.,Ltd.), and general homomixers such as the TK Homomixer Mark II 20(manufactured by Tokushu Kika Kogyo Co., Ltd.) and the TK PipelineHomomixer SL (manufactured by Tokushu Kika Kogyo Co., Ltd.).

The above microcapsulation is preferably conducted at a temperaturehigher than the upper limit temperature (T2) of the melting point rangefor the mixture, and for example, is preferably conducted with theentire system maintained at a temperature within a range from 60 to 80°C.

Once the capsulation is complete, there are absolutely no problemsassociated with solid-liquid or liquid-gas phase changes caused bytemperature variations within the encapsulated material inside thecapsules. This property, wherein the capsules can be treated in the samemanner regardless of whether phase changes have occurred within theencapsulated material, is one of the significant advantages ofmicrocapsules.

Suitable examples of the membrane material used during the in situpolymerization include urea resins, melamine resins, acrylate esters,and polyisocyanates. The use of melamine resins (melamine andformaldehyde), urea-formalin resins (urea and formaldehyde) as themembrane material is particularly preferred.

For example, in those cases where a melamine resin is used as themembrane material, the production is preferably conducted in the mannerdescribed below. First, the volatile substance and the additive aremixed together at a temperature that exceeds the upper limit temperature(T2) of the melting point range for the mixture to be encapsulated, thusforming an encapsulation material (A) (oil phase). In a separatepreparation, in order to enable acceleration and stabilization of theoil droplets of the mixture, ethylene maleic anhydride resin as theemulsion accelerator is dissolved in water, yielding an emulsionaccelerator liquid (B). In another preparation, an aqueous solution (C)of a melamine resin prepolymer is also prepared. At a temperatureexceeding T2, the material (A) is then mixed with the liquid (B) andemulsified to prepare an emulsion, and a stirring number is adjusteduntil the desired average particle size is obtained. The solution (C) isthen added, and stirring is continued, thereby producing a melamineresin membrane around the periphery of the oil droplets of theencapsulation material, and yielding a microcapsule slurry.

The average particle size of the oil droplets within the emulsifiedmixture can be set appropriately in accordance with the desired averageparticle size for the final product microcapsules.

A preferred embodiment in the case of an in situ polymerization using aurea-formalin resin is as described below. First, a urea resin monomer,a resorcin resin monomer, and an ethylene maleic anhydride resin(emulsion accelerator) are dissolved in water. This solution is heatedto a temperature exceeding the upper limit temperature (T2) of themelting point range for the mixture to be encapsulated, an encapsulationmaterial (oil phase) prepared in the same manner as described above isthen added to the solution and emulsified, and stirring is continueduntil the desired average particle size is obtained. Formaldehyde isthen added, and stirring is continued, thereby producing a urea-formalinresin membrane around the periphery of the encapsulation material, andyielding a microcapsule slurry.

Next is a description of a coacervation method. First, the membranematerial is dissolved in a water phase, and the oil phase of theencapsulation material is then added and stirred, thereby dispersing theencapsulation material as fine droplets. To the water phase of the thusobtained O/W dispersion system (emulsion) is gradually added a poorsolvent relative to the membrane material (a liquid that is unable toreadily dissolve the membrane material), thereby lowering the solubilityof the membrane material and causing the membrane material toprecipitate out in a manner that encircles the fine droplets.Alternatively, the temperature of the O/W dispersion system may belowered, thereby lowering the solubility of the membrane material andcausing the precipitation.

In the above description, the W/O dispersion system could also be formedby preparing the membrane material as the oil phase and theencapsulation material as the water phase.

In the case of interfacial polymerization, an oil-soluble membranematerial monomer and a water-soluble monomer that react together to formthe membrane are used. First, an oil phase premix comprising a uniformmixture of the oil-soluble membrane material monomer and theencapsulation material, and a water phase comprising the water-solublemonomer and an emulsion accelerator are prepared. The oil phase premixis then dispersed within the water phase, and the resulting O/W or W/Odispersion system is heated, thereby effecting polymerization at theinterface between the oil phase and the water phase.

The particle size of the microcapsules can be selected in accordancewith their intended usage. Although there are no particularrestrictions, if suitability for a wide variety of potentialapplications is considered, then the average particle size is preferablywithin a range from 0.5 to approximately 100 μm. If the particle size istoo large, then the capsules themselves become prone to rupture, makingthem unsuitable for a variety of applications. In contrast, if theparticle size is too small, the capsules become overly resistant torupture, increasing the danger that the effects of the contents may notmanifest adequately.

For example, in the case of capsule-containing ink or in those caseswhere capsules are blended into fibers, paper, or erasers or the like, asmall particle size of approximately 1 to 20 μm is preferred in terms ofdispersion and processing. In contrast, in applications where capsulesare adhered to the surface of a molded product or the like, and theapplication requires the capsules to be easily ruptured, a largeparticle size of approximately 20 to 100 μm is preferred in terms ofincreasing the frequency of contact and lowering the strength of thecapsules.

Regardless of whether in situ polymerization, interfacialpolymerization, or some other polymerization method is used, the capsuleparticle size can be controlled by altering factors such as therevolution speed and the shape of the stirring blade or rotor blade ofthe stirrer or homomixer used during the emulsification step of themicrocapsulation process, or by adjusting the reaction rate by alteringthe polymerization conditions (such as the reaction temperature andtime) for the membrane material.

Microcapsules can be used for a variety of applications. Techniques forusing the microcapsules include simply adding and dispersing them in thecase of liquid materials, or incorporating the microcapsules by coating,spraying, adhesion or kneading techniques in the case of substrates formanufacturing paper or fabrics.

Microcapsules can be used within a wide range of products, and potentialapplications in those cases where the volatile substance is a fragranceinclude adding the microcapsules to inks, coating materials (bothwater-based and oil-based, for pens or spray-type applications, etc.),cosmetics, air fresheners, deodorants, cleaning agents, and fabricsofteners and the like; spraying or bonding the microcapsules to printedmatter (such as new year greeting cards, catalogues, letter writingpaper, and seals), fabrics, textiles, textile products (such as clothingand towels), and tissue paper; and blending or mixing the microcapsulesinto molded resins, rubber, textiles, and erasers and the like or theraw materials thereof.

The blend quantity of the microcapsules when used in these types ofproducts can be adjusted appropriately in accordance with the desiredproduct characteristics.

Consumer Products

In a first aspect of Applicants' invention, Applicants' inventionincludes a consumer product such as an article and/or cleaning and/ortreatment composition comprising at least 0.00001 weight percent of abenefit agent containing microcapsule according to, any balance of saidcompositions being one or more adjunct materials.

In a second aspect of Applicants' invention, Applicants' inventionincludes a consumer product such as an article and/or cleaning and/ortreatment composition comprising from about 0.00001 to about 99.9 weightpercent, from about 0.00001 to about 10 weight percent, from about 0.02to about 5 weight percent or even from about 0.2 to about 2 weightpercent of a benefit agent containing microcapsule according to thepresent invention, any balance of said compositions being one or moreadjunct materials.

When tested according to test Method 1, the aformentioned aspects ofApplicants' may comprise less than or equal to 50 ppm formaldehyde, lessthan or equal to 25 ppm formaldehyde, less than or equal to 10 ppmformaldehyde or even less than or equal to 5 ppm formaldehyde.

When tested according to test Method 2, the aformentioned aspects ofApplicants' invention may comprise at least 5%, from about 5 to about99%, from about 8 to about 80% or even from about 10 to about 60% water.

If any of the aforementioned aspects of Applicants' invention is anaqueous heavy duty liquid detergent, such detergent may have a pH offrom about 2 to about 12, from about 4 to about 10 or even from about 6to about 9. Otherwise such consumer product may have, when measured byMethod 3, a pH of from about 8 to about 12, from about 8.5 to about 11or even from about 9 to about 11.

Aforementioned aspects of Applicants' invention typically contain anadjunct material that is a surfactant. Such surfactant may be selectedfrom anionic, nonionoic, zwitterionic, cationic and ampholiticsurfactants. Anionic surfactants are typically used in liquid detergentsin levels of from about 1 to about 80, from about 1 to about 50 or evenfrom about 2 to about 20 percent by weight. A representative list ofsurfactants can be found in the adjunct materials section of thisspecification. However, when an anionic surfactant is employed,particularly in a liquid detergent, such as a aqueous liquid detergent,such surfactant may be selected from the group consisting of C₁₁-C₁₈alkyl benzene sulfonate (LAS), primary, branched and random C₁₀-C₂₀sulfates (AS) and mixtures thereof.

Aforementioned aspects of Applicants' invention may contain amicrocapsule of the present invention wherein the encapsulated benefitagent comprises a perfume, or a perfume mixture.

Aforementioned aspects of Applicants' consumer product inventions mayinclude other perfume systems, for example, free perfume, pro-perfumessuch as beta-ketoesters, esters, acetals, oxazolidines, ortho-esters,beta-amino ketones and Schiff Bases, perfume containing zeolite systems,and materials such as cyclodextrins.

Adjunct Materials

While not essential for the purposes of the present invention, thenon-limiting list of adjuncts illustrated hereinafter are suitable foruse in the instant compositions and may be desirably incorporated incertain embodiments of the invention, for example to assist or enhancecleaning performance, for treatment of the substrate to be cleaned, orto modify the aesthetics of the cleaning composition as is the case withperfumes, colorants, dyes or the like. The precise nature of theseadditional components, and levels of incorporation thereof, will dependon the physical form of the composition and the nature of the cleaningoperation for which it is to be used. Suitable adjunct materialsinclude, but are not limited to, surfactants, builders, chelatingagents, dye transfer inhibiting agents, dispersants, enzymes, and enzymestabilizers, catalytic materials, bleach activators, hydrogen peroxide,sources of hydrogen peroxide, preformed peracids, polymeric dispersingagents, clay soil removallanti-redeposition agents, brighteners, sudssuppressors, dyes, perfumes, structure elasticizing agents, fabricsofteners, carriers, hydrotropes, processing aids, solvents and/orpigments. In addition to the disclosure below, suitable examples of suchother adjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282,6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.

As stated, the adjunct ingredients are not essential to Applicants'compositions. Thus, certain embodiments of Applicants' compositions donot contain one or more of the following adjuncts materials:surfactants, builders, chelating agents, dye transfer inhibiting agents,dispersants, enzymes, and enzyme stabilizers, catalytic materials,bleach activators, hydrogen peroxide, sources of hydrogen peroxide,preformed peracids, polymeric dispersing agents, clay soilremoval/anti-redeposition agents, brighteners, suds suppressors, dyes,perfumes, structure elasticizing agents, fabric softeners, carriers,hydrotropes, processing aids, solvents and/or pigments. However, whenone or more adjuncts are present, such one or more adjuncts may bepresent as detailed below:

Bleaching Agents—The cleaning compositions of the present invention maycomprise one or more bleaching agents. Suitable bleaching agents otherthan bleaching catalysts include photobleaches, bleach activators,hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids andmixtures thereof. In general, when a bleaching agent is used, thecompositions of the present invention may comprise from about 0.1% toabout 50% or even from about 0.1% to about 25% bleaching agent by weightof the subject cleaning composition. Examples of suitable bleachingagents include:

(1) photobleaches for example sulfonated zinc phthalocyanine;

(2) preformed peracids: Suitable preformed peracids include, but are notlimited to, compounds selected from the group consisting ofpercarboxylic acids and salts, percarbonic acids and salts, perimidicacids and salts, peroxymonosulfuric acids and salts, for example,Oxzone®, and mixtures thereof. Suitable percarboxylic acids includehydrophobic and hydrophilic peracids having the formula R—(C═O)O—O-Mwherein R is an alkyl group, optionally branched, having, when theperacid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12carbon atoms and, when the peracid is hydrophilic, less than 6 carbonatoms or even less than 4 carbon atoms; and M is a counterion, forexample, sodium, potassium or hydrogen;

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof. In one aspect ofthe invention the inorganic perhydrate salts are selected from the groupconsisting of sodium salts of perborate, percarbonate and mixturesthereof. When employed, inorganic perhydrate salts are typically presentin amounts of from 0.05 to 40 wt %, or 1 to 30 wt % of the overallcomposition and are typically incorporated into such compositions as acrystalline solid that may be coated. Suitable coatings include,inorganic salts such as alkali metal silicate, carbonate or borate saltsor mixtures thereof, or organic materials such as water-soluble ordispersible polymers, waxes, oils or fatty soaps; and

(4) bleach activators having R—(C═O)-L wherein R is an alkyl group,optionally branched, having, when the bleach activator is hydrophobic,from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when thebleach activator is hydrophilic, less than 6 carbon atoms or even lessthan 4 carbon atoms; and L is leaving group. Examples of suitableleaving groups are benzoic acid and derivatives thereof—especiallybenzene sulphonate. Suitable bleach activators include dodecanoyloxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyloxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzenesulphonate, tetraacetyl ethylene diamine (TAED) and nonanayloxybenzenesulphonate (NOBS). Suitable bleach activators are also disclosed in WO98/17767. While any suitable bleach activator may be employed, in oneaspect of the invention the subject cleaning composition may compriseNOBS, TAED or mixtures thereof.

When present, the peracid and/or bleach activator is generally presentin the composition in an amount of from about 0.1 to about 60 wt %, fromabout 03 to about 40 wt % or even from about 0.6 to about 10 wt % basedon the composition. One or more hydrophobic peracids or precursorsthereof may be used in combination with one or more hydrophilic peracidor precursor thereof.

The amounts of hydrogen peroxide source and peracid or bleach activatormay be selected such that the molar ratio of available oxygen (from theperoxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1.

Surfactants—The cleaning compositions according to the present inventionmay comprise a surfactant or surfactant system wherein the surfactantcan be selected from nonionic surfactants, anionic surfactants, cationicsurfactants, ampholytic surfactants, zwitterionic surfactants,semi-polar nonionic surfactants and mixtures thereof. When present,surfactant is typically present at a level of from about 0.1% to about80%, from about 1% to about 50% or even from about 5% to about 40% byweight of the subject composition.

Builders—The cleaning compositions of the present invention may compriseone or more detergent builders or builder systems. When a builder isused, the subject composition will typically comprise at least about 1%,from about 5% to about 60% or even from about 10% to about 40% builderby weight of the subject composition. Builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates, alkali metal silicates, alkaline earth and alkali metalcarbonates, aluminosilicate builders and polycarboxylate compounds,ether hydroxypolycarboxylates, copolymers of maleic anhydride withethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, thevarious alkali metal, ammonium and substituted ammonium salts ofpolyacetic acids such as ethylenediamine tetraacetic acid andnitrilotriacetic acid, as well as polycarboxylates such as melliticacid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid,benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, andsoluble salts thereof.

Chelating Agents—The cleaning compositions herein may contain achelating agent. Suitable chelating agents include copper, iron and/ormanganese chelating agents and mixtures thereof. When a chelating agentis used, the subject composition may comprise from about 0.005% to about15% or even from about 3.0% to about 10% chelating agent by weight ofthe subject composition.

Dye Transfer Inhibiting Agents—The cleaning compositions of the presentinvention may also include one or more dye transfer inhibiting agents.Suitable polymeric dye transfer inhibiting agents include, but are notlimited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in a subject composition, the dye transfer inhibiting agents maybe present at levels from about 0.0001% to about 10%, from about 0.01%to about 5% or even from about 0.1% to about 3% by weight of thecomposition.

Brighteners—The cleaning compositions of the present invention can alsocontain additional components that may tint articles being cleaned, suchas fluorescent brighteners. Suitable fluorescent brightener levelsinclude lower levels of from about 0.01, from about 0.05, from about 0.1or even from about 0.2 wt % to upper levels of 0.5 or even 0.75 wt %.

Dispersants—The compositions of the present invention can also containdispersants. Suitable water-soluble organic materials include the homo-or co-polymeric acids or their salts, in which the polycarboxylic acidcomprises at least two carboxyl radicals separated from each other bynot more than two carbon atoms.

Enzymes—The cleaning compositions can comprise one or more enzymes whichprovide cleaning performance and/or fabric care benefits. Examples ofsuitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, mannanases, pectate lyases,keratinases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase,and amylases, or mixtures thereof. A typical combination is an enzymecocktail that may comprise, for example, a protease and lipase inconjunction with amylase. When present in a cleaning composition, theaforementioned enzymes may be present at levels from about 0.00001% toabout 2%, from about 0.0001% to about 1% or even from about 0.001% toabout 0.5% enzyme protein by weight of the composition.

Enzyme Stabilizers—Enzymes for use in detergents can be stabilized byvarious techniques. The enzymes employed herein can be stabilized by thepresence of water-soluble sources of calcium and/or magnesium ions inthe finished compositions that provide such ions to the enzymes. In caseof aqueous compositions comprising protease, a reversible proteaseinhibitor, such as a boron compound, can be added to further improvestability.

Catalytic Metal Complexes—Applicants' cleaning compositions may includecatalytic metal complexes. One type of metal-containing bleach catalystis a catalyst system comprising a transition metal cation of definedbleach catalytic activity, such as copper, iron, titanium, ruthenium,tungsten, molybdenum, or manganese cations, an auxiliary metal cationhaving little or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid,ethylenediaminetetra(methylenephosphonic acid) and water-soluble saltsthereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

-   If desired, the compositions herein can be catalyzed by means of a    manganese compound. Such compounds and levels of use are well known    in the art and include, for example, the manganese-based catalysts    disclosed in U.S. Pat. No. 5,576,282.-   Cobalt bleach catalysts useful herein are known, and are described,    for example, in U.S. Pat. No. 5,597,936; U.S. Pat. No. 5,595,967.    Such cobalt catalysts are readily prepared by known procedures, such    as taught for example in U.S. Pat. No. 5,597,936, and U.S. Pat. No.    5,595,967.-   Compositions herein may also suitably include a transition metal    complex of ligands such as bispidones (WO 05/042532 A1) and/or    macropolycyclic rigid ligands—abbreviated as “MRLs”. As a practical    matter, and not by way of limitation, the compositions and processes    herein can be adjusted to provide on the order of at least one part    per hundred million of the active MRL species in the aqueous washing    medium, and will typically provide from about 0.005 ppm to about 25    ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm    to about 5 ppm, of the MRL in the wash liquor.-   Suitable transition-metals in the instant transition-metal bleach    catalyst include, for example, manganese, iron and chromium.    Suitable MRLs include    5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.-   Suitable transition metal MRLs are readily prepared by known    procedures, such as taught for example in WO 00/32601, and U.S. Pat.    No. 6,225,464.

Solvents—Suitable solvents include water and other solvents such aslipophilic fluids. Examples of suitable lipophilic fluids includesiloxanes, other silicones, hydrocarbons, glycol ethers, glycerinederivatives such as glycerine ethers, perfluorinated amines,perfluorinated and hydrofluoroether solvents, low-volatilitynonfluorinated organic solvents, diol solvents, otherenvironmentally-friendly solvents and mixtures thereof.

Processes of Making Consumer Products The products of the presentinvention can be formulated into any suitable form and prepared by anyprocess chosen by the formulator, non-limiting examples of which aredescribed in Applicants' examples and in U.S. Pat. No. 5,879,584; U.S.Pat. No. 5,691,297; U.S. Pat. No. 5,574,005; U.S. Pat. No. 5,569,645;U.S. Pat. No. 5,565,422; U.S. Pat. No. 5,516,448; U.S. Pat. No.5,489,392; U.S. Pat. No. 5,486,303 all of which are incorporated hereinby reference. When benefit agent containing microcapsules areincorporated into a consumer product, such microcapsules may need to befurther processed. Such processing typically entails homogenizing theliquid capsule slurry by mixing or stirring, adding water to the capsuleslurry, adding a structuring agent to the capsule slurry, adjusting thedensity of the capsule content, adding a dispersant or aanti-sedimentation to the capsule slurry or a mixture thereof. Suchprocessing typically depends on the requirements of the formulationand/or article that will comprise the benefit containing microcapsule.In certain cases the microcapsules may be embedded in a consumer productwhen the consumer product is produced or formed and/or adhered to thesurface of such consumer product by physical and/or chemical meansincluding gluing.

Method of Use

The present invention includes a method for cleaning and/or treating asitus inter alia a surface or fabric. Such method includes the steps ofcontacting an embodiment of Applicants'consumer product, if acomposition in neat form or diluted in a wash liquor, with at least aportion of a surface or fabric then optionally rinsing such surface orfabric. The surface or fabric may be subjected to a washing step priorto the aforementioned rinsing step. For purposes of the presentinvention, washing includes but is not limited to, scrubbing, andmechanical agitation. As will be appreciated by one skilled in the art,the consumer products of the present invention are ideally suited foruse in a variety of applications including cleaning or treating asurface for example in a laundry application. Accordingly, the presentinvention includes a method for laundering a fabric. The methodcomprises the steps of contacting a fabric to be laundered with a saidcleaning laundry solution comprising at least one embodiment ofApplicants' cleaning composition, cleaning additive or mixture thereof.The fabric may comprise most any fabric capable of being laundered innormal consumer use conditions. The solution preferably has a pH of fromabout 8 to about 10.5. The compositions may be employed atconcentrations of from about 500 ppm to about 15,000 ppm in solution.The water temperatures typically range from about 5° C. to about 90° C.The water to fabric ratio is typically from about 1:1 to about 30:1.

Test Methods

-   Method 1: Formaldehyde is analyzed by means of a derivatization    specific to aldehydes and carbonyl compounds. This is accomplished    via room temperature derivatization with 2,4-Di Nitro Phenyl    Hydrazine (DNPH) prior to a chromatographic separation using    Reversed Phase Chromatography with UVIVis detection (wavelength    setting=365 nm). Calibration is performed through “External Standard    calibration” with reference formaldehyde solutions made up from    commercially available 36-37% Formaldehyde solution. Activity of    this material can be determined via a redox titration.-   Method 2: ASTM E203-01 via Karl Fischer titration method.-   Method 3: pH is determined by Health Canada's method “Determination    of the pH of Consumer Products in Aqueous Solution” Product Safety    Reference Manual, Book 5—Laboratory Policies and Procedures    Effective 2001 Oct. 28 Part B: Test Methods Section, Method C-13    Amendment #29-   Method 4. Procedure For Determination Of % Perfume Leakage-   When determining the % perfume leakage from perfume microcapsules in    liquid detergent, a fresh sample of liquid detergent with equal    level of free perfume (without Perfume Microcapsules) must also be    analysed in parallel for reference.    -   1. Preperation Of Internal Standard Solution        -   Stock solution of tonalid: Weigh 70 mg tonalid and add 20 ml            hexane p.a.        -   Internal Standard Solution solution: Dilute 200 μl of stock            solution in 20 ml hexane p.a.        -   Mix to homogenize    -   2. Perfume Extraction From Liquid Detergent Without Perfume        Microcapsules (Reference)        -   Weigh 2 g of liquid detergent product into an extraction            vessel        -   Add 2 ml of ethanol and 1 ml of deionised water        -   Shake gentle to homogenize        -   Add 2 ml of Internal Standard Solution and close vessel        -   Extract perfume by gently turning the extraction vessel            upside-down for 20 times (manually)        -   Add spoon tip of Sodium Sulphate        -   After separation of layers, immediately transfer            hexane-layer into Gas Chromatograph auto sampler-vial and            cap vial        -   Inject splitless (1.5 μl) into Gas Chromatograph            injection-port        -   Run Gas Cromatographic-Mass Spectrometric analysis: Gas            Chromatographic separation on Durawax-4 (60 m, 0.32 mm ID,            0.25 μm Film) 40° C./4° C./min/230° C./20′    -   3. Perfume Extraction From Liquid Detergent With Perfume        Microcapsules        -   Weigh 20 g of liquid detergent product into a centrifuge            vessel of 50 ml        -   Centrifuge for 5 min at 3500 rpm        -   Take 2 g of the liquid layer (lower layer), avoid contact            with upper capsules layer        -   Add 2 ml of ethanol and 1 ml of deionised water        -   Shake gentle to homogenize        -   Add 2 ml of Internal Standard Solution and close vessel        -   Extract perfume by gently turning the extraction vessel            upside-down for 20 times (manually)        -   Add spoon tip of Sodium Sulphate        -   After separation of layers, immediately transfer            hexane-layer into Gas Chromatograph auto sampler-vial and            cap vial        -   Inject splitless (1.5 μl) into Gas Chromatograph            injection-port        -   Run Gas Chromatographic-Mass Spectrometric analysis: Gas            Chromatographic separation on Durawax-4 (60 m, 0.32 mm ID,            0.25 μm Film) 40° C./4° C./min/230° C./20′    -   4. Calculation: The perfume leakage from capsules per individual        Perfume Raw Material:

Area Perfume Raw Material caps×Area Internal Standard Solutionref×Weight ref×100%

% perfume leakage=Area Internal Standard Solution caps×Area Perfume RawMaterial ref×Weight caps

Examples

As follows is a more detailed description of the present invention basedon a series of examples, although the present invention is in no wayrestricted to the examples presented below. In the followingdescription, the units “% by weight” and “parts by weight” areabbreviated as “%” and “parts” respectively when referring tomicrocapsule inventions.

Example 1 Production of Melamine Resin Membrane/Fragrance Microcapsules(In Situ Polymerization Method)

-   (A) Preparation of encapsulation material (mixture): A mixture    comprising 75% of a mint fragrance (X-7028, manufactured by Takasago    International Corporation, this also applies to all subsequent    references to mint) and 25% of palmitic acid (melting point: 63° C.)    is stirred at 70° C., thereby dissolving the palmitic acid in the    fragrance. The melting point range (T1−T2) for the resulting mixture    is from 5 to 45° C. (confirmed visually). The mixture is held at    55° C. to prevent it solidifying prior to emulsification.-   (B) Preparation of emulsion accelerator liquid: 15% of ethylene    maleic anhydride resin (Scripset-520, manufactured by Monsanto    Company) and 85% of water are mixed together at 60° C., and the    mixture is adjusted to pH 4 using acetic acid.-   (C) Preparation of aqueous solution of melamine resin prepolymer:    15% of a melamine-formaldehyde resin (Sumirez Resin 615K,    manufactured by Sumitomo Chemical Co., Ltd.) is dissolved in 85% of    water at 60° C.-   (D) Capsulation: 100 parts of the above emulsion accelerator    liquid (B) is stirred at 60° C. at 3,000 rpm using a TK Homomixer    Mark II 20 (manufactured by Tokushu Kika Kogyo Co., Ltd.), 100 parts    of the above encapsulation material (A) is added and emulsified, the    rotational speed is then gradually raised, and stirring is conducted    at 7,000 rpm for 30 minutes, yielding an emulsion in which the    average particle size of the oil droplets of the encapsulation    material is approximately 3 μm (as measured by a laser diffraction    particle size analyzer SALD-3100 (manufactured by Shimadzu    Corporation), this analyzer is also used to measure all subsequent    particle sizes).

To this emulsion is added 50 parts of the above melamine resinprepolymer aqueous solution (C), and stirring is continued for 2 hours,thus generating a melamine resin membrane around the periphery of theencapsulation material, and forming a microcapsule slurry with a solidfraction concentration of approximately 40%.

Example 2 Production of Melamine Resin Membrane/Fragrance Microcapsules(In Situ Polymerization Method)

An encapsulation material (A) is prepared by mixing 75% of the mintfragrance and 25% of behenyl alcohol (melting point: 70° C.) at 75° C.,thereby dissolving the behenyl alcohol in the fragrance and forming amixture. The melting point range for the thus obtained mixture is from10 to 50° C. The mixture is held at 60° C. to prevent it solidifyingprior to emulsification.

With the exception of using this encapsulation material (A), amicrocapsule slurry with a solid fraction concentration of approximately40% is prepared in the same manner as the Example 1.

Example 3 Production of Melamine Resin Membrane/Fragrance Microcapsules(In Situ Polymerization Method)

An encapsulation material (A) is prepared by mixing 65% of the mintfragrance and 35% of paraffin wax (EMW-0003, manufactured by NipponSeiro Co., Ltd., melting point: 50° C.) at 60° C., thereby dissolvingthe paraffin wax in the fragrance and forming a mixture. The meltingpoint range for the thus obtained mixture is from 0 to 40° C. Themixture is held at 50° C. to prevent it solidifying prior toemulsification.

With the exception of using this encapsulation material (A), amicrocapsule slurry with a solid fraction concentration of approximately40% is prepared in the same manner as the example 1.

Example 4 Production of Urea-Formalin Resin Membrane/FragranceMicrocapsules (In Situ Polymerization Method)

10% of a urea resin monomer (reagent grade, manufactured by NissanChemical Industries, Ltd.), 2% of a resorcin resin monomer (reagentgrade, manufactured by Mitsui Chemicals, Inc.), and 3% of an ethylenemaleic anhydride resin (Scripset-520, manufactured by Monsanto Company)are dissolved in 85% of water, and the solution is adjusted to pH 3using acetic acid.

50 parts of the thus obtained aqueous solution is heated to 60° C., 40parts of the same encapsulation material as the example 1 is added andemulsified, and stirring is conducted for approximately 30 minutes,until oil droplets with an average particle size of 3 μm had beenformed. To this emulsion is added 10 parts of formaldehyde, and stirringis then continued for 2 hours, thus generating a urea-formalin resinaround the periphery of the encapsulation material, and forming amicrocapsule slurry with a solid fraction concentration of approximately40%.

Example 5 Production of Gelatin-Gum Arabic Membrane/FragranceMicrocapsules (Coacervation Method)

Gelatin (APH, manufactured by Nitta Gelatin Inc.) is dissolved in waterto produce an aqueous solution with a gelatin concentration of 3.6%, andthe solution is adjusted to pH 6 using acetic acid. To 30 parts of thisaqueous solution is added 25 parts of a 3.6% aqueous solution of gumArabic (reagent grade, manufactured by Gokyo Trading Co., Ltd.), therebypreparing an aqueous solution for forming the microcapsule membrane. 55parts of this aqueous solution is heated to approximately 60° C., the pHis adjusted to 5, 40 parts of the same encapsulation material as theexample 1 is added and emulsified, and stirring is continued until oildroplets with an average particle size of approximately 5 μm had beenformed.

The resulting emulsion/dispersion is cooled gradually to 10° C., thusgenerating a gelatin-gum Arabic polymer membrane around the periphery ofthe encapsulation material. 5 parts of a 25% aqueous solution ofglutaraldehyde (reagent grade, manufactured by Daicel ChemicalIndustries, Ltd.) is then added, and the polymer membrane is cured, thusyielding a microcapsule slurry with a solid fraction concentration ofapproximately 40%.

Comparative Example 1

With the exception of altering the encapsulation material (A) to 100% ofthe mint fragrance, a microcapsule slurry with a solid fractionconcentration of approximately 40% is prepared in the same manner as theExample 1.

Comparative Example 2

An encapsulation material (A) is prepared by mixing 75% of the mintfragrance and 25% of phthalic acid (melting point: 234° C.) at 240° C.,thereby dissolving the phthalic acid in the mint fragrance and forming amixture. The melting point range for the thus obtained mixture is from60 to 90° C. The mixture is held at 90° C. or higher to prevent itsolidifying prior to emulsification.

An attempt is made to capsulate the encapsulation material in the samemanner as the example 1, with the temperature of the emulsionaccelerator liquid (B) held at as high a temperature as possible (90° C.or higher), but during the emulsification step, the mixture solidifiedand precipitated out, meaning an emulsion could not be obtained, andcapsulation could not be completed.

Comparative Example 3

An encapsulation material (A) is prepared by mixing 75% of the mintfragrance and 25% of diethyl phthalate (fixative, melting point: −40°C.), thus forming a liquid mixture. This mixture remained a liquid evenat −20° C. Using this liquid, microcapsulation is conducted in the samemanner as the example 1, yielding a microcapsule slurry with a solidfraction concentration of approximately 40%.

Comparative Example 4

The non-capsulated, neat mint fragrance liquid (100%) is used forcomparison.

Using the microcapsules obtained in the examples 1 to 5 and thecomparative examples 1 and 3, as well as the neat fragrance liquid fromthe comparative example 4, the following evaluations are conducted.

(1) Capsulation Achievability

Mixtures for which capsulation is possible are evaluated as “A”, andthose for which capsulation is impossible evaluated as “C”.

(2) Strength of Aroma Immediately Following Printing

50 parts of the obtained microcapsule slurry are added to 50 parts of awater-based binder (Vondic 1980NS, a water-dispersed urethane resin,manufactured by Dainippon Ink and Chemicals, Incorporated, solidfraction: 45%), thus forming a water-based screen ink.

This ink is printed onto high quality paper using a 100-mesh screenplate made of a PET Film (Tetlon®, manufactured by Teijin DuPont Films,print surface area: 3 cm×3 cm), and then dried for 24 hours at roomtemperature.

The surface of each of the printed materials is scratched lightly withfingernails using 10 back and forth movements, and the strength of themint aroma is evaluated. Because the comparative example 4 is simply theneat fragrance liquid, it could not be mixed with the water-basedbinder, and so the aroma of the neat liquid is evaluated.

Evaluation is conducted by sensory assessment using a mixed gender panelof 5 panelists. The printed material is brought gradually closer to thenose, the maximum distance (cm) at which the aroma could be detected ismeasured, and then points are awarded based on the following criteria.12 cm or greater: 5 points (the aroma is detectable even when 12 cm orfurther from the nose), 9 cm or greater but less than 12 cm: 4 points, 6cm or greater but less than 9 cm: 3 points, 3 cm or greater but lessthan 6 cm: 2 points, 0 cm or greater but less than 3 cm: 1 point, and 0points if the aroma is undetectable even on contact (even at 0 cm). Themaximum possible score is 25 points.

(3) Strength of Aroma After Standing for 1 Week at 40° C. FollowingPrinting

Each of the printed materials from (2) above is left to stand for 1 weekat 40° C., and then, once again, the surface of the printed material isscratched lightly with fingernails using 10 back and forth movements,and the strength of the mint aroma is evaluated in the same manner asdescribed in (2) above.

(4) Stability within Organic Solvent

Each of the produced microcapsule slurries is powdered using a spraydryer, yielding a microcapsule powder.

30 parts of this powder is added to 70 parts of toluene, and the mixtureis stored in a sealed container for 1 week at 25° C. Subsequently, thetoluene is evaporated off under room temperature conditions. In the caseof the comparative example 4, 30 parts of the neat fragrance liquid isadded directly to 70 parts of toluene.

The microcapsules remaining after the evaporation are ruptured byscratching lightly with fingernails using 10 back and forth movements,and the strength of the aroma is evaluated in the same manner asdescribed in (2) above.

The results obtained are shown in Table 1.

TABLE 1 Strength of Strength of aroma aroma Stability Capsulationimmediately following 1 in organic achievability after printing week at40° C. solvent Example 1 A 21 19 19 Example 2 A 21 20 19 Example 3 A 2018 18 Example 4 A 21 19 18 Example 5 A 22 15 14 Comparative A 22 7 7Example 1 Comparative C — — — Example 2 Comparative A 22 9 8 Example 3Comparative — 25 1 0 Example 4

As is evident from Table 1, the microcapsules of the Examples 1 to 5enabled the aroma of the fragrance to be favorably retained. This isbecause at conditions of 40° C., the encapsulated material is asemisolid, enabling the volatility of the fragrance to be suppressed.Furthermore, the microcapsules also exhibited no interaction with thetoluene of the external phase, and are able to be mixed in a stablemanner.

In contrast, in both the Comparative Examples 1 and 3, because theencapsulated material is a liquid, it gradually escaped through the finepores in the melamine resin membrane, meaning the aroma could not beretained over an extended period. Furthermore, in the organic solvent,it is thought that because the encapsulated material is a liquid, amechanism that seeks to achieve co-solubility with the toluene draws theliquid fragrance out into the external phase.

In the comparative Example 4, the neat fragrance liquid volatilized atthe same time as the evaporation of the toluene.

The comparative example 3 represents an example in which aconventionally used fixative is used to suppress volatilization of thefragrance and prolong the retention of the aroma. Examples of typicalfixatives include benzyl alcohol (melting point: 15° C.), benzylbenzoate (melting point: 21° C.), triethylene citrate (melting point:−55° C.), and dipropylene glycol (melting point: −40° C.), and all ofthese have a melting point lower than 25° C., meaning they are unable toform a semisolid in the range from −20 to 60° C.

In the comparative example 2, although the encapsulation material neededto remain a liquid during the emulsification step of themicrocapsulation, it is thought that microcapsulation could not beachieved because it proved impossible to maintain the temperature ofboth the emulsion accelerator liquid and the emulsion at a temperatureexceeding the upper limit temperature (T2=90° C.) for the mixturemelting point range.

The evaluation score for the example 5 is lower than those for theexamples 1 to 4, and it is thought that this reflects the fact that theairtightness of the gelatin-gum Arabic of the capsule membrane is lowerthan that of both the melamine resin and the urea-formalin resin.However, the results for the example 5 are still vastly superior tothose of the comparative examples.

Consumer Product Examples

The following definitions are used in the consumer product examples thatare given below. Any of the consumer product examples given below maycomprises one or more of the microcapsules that is claimed or disclosedin this specification.

-   LAS Sodium linear C₁₁₋₁₃ alkylbenzene sulphonate.-   CxyAS Sodium C_(1x)-C_(1y) alkyl sulfate.-   CxyEzS C_(1x)-C_(1y) sodium alkyl sulfate condensed with an average    of z moles of ethylene oxide.-   CxEOy Cx alcohol with an average of ethoxylation of y-   QAS R₂.N+(CH₃)₂(C₂H₄OH) with R₂═C₁₀-C₁₂-   Soap Sodium linear alkyl carboxylate derived from a 80/20 mixture of    tallow and coconut fatty acids.-   Silicate Amorphous Sodium Silicate (SiO₂:Na₂O ratio=1.6-3.2:1).-   Zeolite A Hydrated Sodium Aluminosilicate of formula    Na₁₂(AlO₂SiO₂)₁₂.27H₂O having a primary particle size in the range    from 0.1 to 10 micrometers (Weight expressed on an anhydrous basis).-   (Na-)SKS-6 Crystalline layered silicate of formula δ-Na₂Si₂O₅.-   Citrate Tri-sodium citrate dihydrate.-   Citric Anhydrous citric acid.-   Carbonate Anhydrous sodium carbonate.-   Sulphate Anhydrous sodium sulphate.-   MA/AA Random copolymer of 4:1 acrylate/maleate, average molecular    weight about 70,000-80,000.-   AA polymer Sodium polyacrylate polymer of average molecular weight    4,500.-   PB1/PB4 Anhydrous sodium perborate monohydrate/tetrahydrate.-   PC3 Anhydrous sodium percarbonate [2.74 Na₂CO₃.3H₂O₂]-   TAED Tetraacetyl ethylene diamine.-   NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.-   DTPA Diethylene triamine pentaacetic acid.-   HEDP Hydroxyethane di phosphonate-   HEDMP Hydroxyethane di(methylene)phosphonate-   DETPMP Diethyltriamine penta(methylene)phosphonate-   EDDS Na salt of Ethylenediamine-N,N′-disuccinic acid, (S,S) isomer-   Protease Proteolytic enzyme sold under the tradename Savinase®,    Alcalase®, Everlase®, by Novozymes A/S, Properase®, Purafect®,    Purafect MA® and Purafect Ox® sold by Genencor and proteases    described in patents WO 91/06637 and/or WO 95/10591 and/or EP 0 251    446.-   Amylase Amylolytic enzyme sold under the tradename Purastar®,    Purafect Oxam® sold by Genencor; Termamyl®, Fungamyl® Duramyl®,    Stainzyme® and Natalase® sold by Novozymes A/S-   Lipase Lipolytic enzyme sold under the tradename Lipolase® Lipolase    Ultra® by Novozymes A/S.-   Cellulase Cellulytic enzyme sold under the tradename Carezyme®,    Celluzyme® and/or Endolase® by Novozymes A/S or a Glucanase enzyme-   Pectate Lyase Pectawash®, Pectaway® sold by Novozymes-   Mannanase Mannaway® sold by Novozymes-   CMC or HEC Carboxymethyl or Hydroxyethyl or ester modified    cellulose. or EMC-   SS Agglom. 12% Silicone/silica, 18% stearyl alcohol, 70% starch in    granular form [suds suppressor agglomerate].-   TEPAE Tetreaethylenepentaamine ethoxylate.-   Photobleach Sulfonated zinc phtalocyanine-   Microcapsule Aqueous slurry containing perfume loaded capsules-   pH Measured as a 1% solution in distilled water at 20° C.-   MEA borate Monoethanolamine borate-   HCl Hydrogen Chloride-   SRP Soil Removal Polymer-   PVNO polyvinylpyridine N-oxide

Example #6

Bleaching high duty laundry detergent compositions are prepared:

I II III IV V VI VII VIII Blown Powder Zeolite A 13.65 13.65 — — — — — —Na Sulfate 22.67 22.67 24.43 30.13 — — — — LAS 6.21 6.21 5.65 — — — — —QAS — — — 2.95 — — — — MA/AA 1.42 1.42 3.50 4.25 — — — — EDDS 0.19 0.190.19 0.23 — — — — Brightener 0.07 0.07 0.06 0.08 — — — — Mg Sulfate 0.650.65 0.39 0.48 — — — — HEDMP 0.17 0.17 0.17 0.21 — — — — Agglomerate 1QAS — — 0.9 — — — — — Carbonate — — 2.45 — — — — — Na Sulfate — — 2.45 —— — — — Agglomerate 2 C₁₄₋₁₅EO₇ — — 2.79 2.21 — — — — Na Sulfate — —6.65 6.84 — — — — Agglomerate 3 LAS — — — — 13.63 14.96 — 13.63 ZeoliteA — — — — 21.42 23.51 — 21.42 Agglomerate 4 LAS — — — — — — 8.12 — NaSulfate — — — — — — 23.54 — Na Carbonate — — — — — — 8.12 — Dryadditives LAS — — 6.40 — — — — — MA/AA — — 0.89 0.89 0.95 0.95 0.99 0.95(particle) TAED 3.58 3.58 3.80 2.70 5.89 5.89 6.14 — NOBS — — — — — — —5.50 LAS (flakes) — — — 27.0 — — — — Silicate R 2.0 3.85 3.85 3.85 2.80— — — — Citric/Citrate 3.58 3.58 3.58 3.58 3.80 3.80 3.96 3.80 NaCarbonate 7.72 7.72 13.84 — 12.35 — 12.87 12.35 HEDP — — — — 0.48 0.480.50 0.48 PC3 or PB1 11.01 11.01 11.01 8.00 8.55 8.55 8.91 8.55 Protease0.009 0.009 0.009 0.009 0.039 0.039 0.039 0.039 Amylase 0.005 0.0050.005 0.005 0.013 0.013 0.013 0.013 Lipase — — — — 0.002 0.002 0.0020.002 Pectate lyase — — — — 0.003 0.003 0.003 0.003 Cellulase 0.003 —0.001 — 0.0005 — — — SS agglom. 0.36 0.36 0.36 0.55 0.62 0.62 0.64 0.62Soap 0.40 0.40 0.40 0.40 0.48 0.48 0.50 0.48 Brightener — — — — 0.100.10 0.10 0.10 Na Sulfate 4.48 4.48 — — 14.30 22.85 14.90 14.30 Spray-onC₁₂₋₁₄EO₇ 4.00 4.00 — — 3.00 3.00 1.00 3.00 Microcapsule 1 0.8 2.0 1.50.7 1.2 0.3 0.2 0.1 Microcapsule 2 — — — — 0.5 1.0 — — Density (g/L) 600600 600 600 800 800 800 800

Example #7

The following laundry compositions, which can be in the form of granulesor tablet, are prepared according to the present invention.

Base Product I II III IV V C₁₄-C₁₅ AS/Tallow AS 8.0 5.0 3.0 3.0 3.0 LAS8.0 — 8.0 — 7.0 C₁₂C₁₅AE₃S 0.5 2.0 1.0 — — C₁₂C₁₅AE₅/AE₃ 2.0 — 5.0 2.02.0 QAS — — — 1.0 1.0 Zeolite A 20.0 18.0 11.0 — 10.0 (Na—)SKS-6 (I) — —9.0 — — (dry add) MA/AA 2.0 2.0 2.0 — — AA polymer — — — — 4.0 Citrate —2.0 — — — Citric 2.0 — 1.5 2.0 — DTPA 0.2 0.2 — — — EDDS — — 0.5 0.1 —HEDP — — 0.2 0.1 — PB1 3.0 5.0 10.0 — 4.0 Percarbonate — — — 18.0 — NOBS3.0 4.0 — — 4.0 TAED — — 2.0 5.0 — Carbonate 15.0 18.0 8.0 15.0 15.0Sulphate 5.0 12.0 2.0 17.0 3.0 Silicate — 1.0 — — 8.0 Microcapsule 0.50.2 1.3 0.7 2.0 Protease 0.033 0.033 0.033 0.046 0.033 Lipase 0.0080.008 0.008 0.008 0.006 Amylase 0.001 0.001 0.001 0.0014 0.001 Cellulase0.0014 0.0014 0.0014 0.01 —

Example #8

The following granular detergents are prepared:

I II III IV V VI VII LAS 7.23 8.46 6.50 7.09 11.13 16.0 16.0 QAS 0.75 —0.60 0.60 1.00 — — C₁₄₋₁₅EO₇ 3.50 5.17 3.50 3.70 3.50 — — C₁₂₋₁₄AE₃S0.25 — — — — 0.70 1.0 C₁₂₋₁₄—N⁺(CH₃)₂(C2H₄OH) — — — — — 0.50 0.50 Natripolyphosphate 18.62 25.00 18.62 24.00 45.00 15.0 18.0 Zeolite A — —0.79 — — 0.18 0.3 Citric acid 1.29 — 1.29 — — — — Sodium Silicate 3.108.00 4.26 3.87 10.00 8.0 6.0 Sodium Carbonate 18.04 11.00 18.04 18.980.42 14.5 16.0 Sulfate 17.58 3.98 19.93 15.48 10.13 30.0 30.0 CMC — — —— — 0.20 0.20 AA/MA 2.15 1.50 1.85 1.60 1.94 0.1 0.05 AA polymer — — — —— — 1.20 Amine ethoxylate polymer 0.60 — 0.49 — — — 1.25 Cyclicpolyamine polymer 0.07 — 0.07 — — — — Percarbonate 13.15 — 10.77 — — — —PB1/PB4 — 9.0/9.0 — 10.45/0 2.37/0 — — TAED 2.50 5.00 1.58 1.52 0.66 — —DTPA 0.34 0.34 0.37 0.39 0.24 0.30 0.30 Mg Sulfate 1.37 1.43 1.37 1.410.58 — — Protease 0.005 0.011 0.006 — — 0.006 0.003 Amylase 0.001 0.0030.001 0.001 — — 0.001 Cellulase 0.0003 0.0002 0.0003 0.0003 — — —Brightener 0.10 0.17 0.08 0.08 0.08 0.23 0.15 Microcapsule 1 0.6 1.2 1.50.2 0.1 1.9 0.7 Microcapsule 2 — — — 0.5 1.8 — —

Example #9

The following granular fabric detergent compositions which provide“softening through the wash” are Prepared:

I II III IV C₁₂₋₁₅AS 0.3 3.43 2.52 1.05 LAS 11.0 5.3 6.55 7.81C₁₂₋₁₄AE₃S — 0.74 0.33 — LAS (mid branched) — — 1.71 1.37 C₁₄₋₁₅EO₇ —2.00 2.00 2.00 QAS — 1.57 1.20 1.35 Citric acid 2.5 1.28 1.28 1.28(Na—)SKS-6 4.0 4.71 4.96 4.71 Zeolite A 12.0 13.51 11.31 15.6Percarbonate 6.5 9.03 9.03 10.3 TAED 1.5 2.48 2.48 3.22 EDDS 0.1 0.1 0.10.1 HEDP 1.2 0.20 0.20 0.20 Smectite clay 10.0 — 13.84 — Polyethyleneoxide 0.2 0.22 0.22 — (MW approx. 300,000) Microcapsule 1 0.5 0.4 0.31.7 Microcapsule 2 — 0.3 — — Protease 0.011 0.009 0.009 0.009 Amylase0.002 0.001 0.001 0.001 Cellulase — 0.0006 0.0006 0.0006 Na Carbonate25.0 29.68 30.52 28.30 Magnesium Sulfate 0.1 0.03 0.03 0.03 Sudssuppressor 1.0 1.0 1.0 1.0 EMC — 1.10 1.10 1.10 HEC 0.8 — — — Sodiumsulfate 18.0 balance balance Balance

Example #10

The following liquid detergent formulations are prepared:

I II III IV V VI LAS 7.8 12.2 4.4 12.2 5.7 1.3 Sodium alkyl — — 14.4 —9.2 5.4 ether sulfate Alkyl ethoxylate 5.7 8.8 2.2 8.8 8.1 3.4Amineoxide 1.0 1.5 0.7 1.5 — — Fatty acid 5.3 8.3 3.0 8.3 — — Citricacid (50%) 1.1 6.8 2.0 3.4 1.9 1.0 Ca and Na formate — — 0.2 — — — Nacumene 0.8 2 — 2.0 — — sulphonate Borate — — 1.5 2.4 2.9 — MEA borate1.5 2.4 — — — — Na hydroxide 3.2 3.2 3.0 4.9 1.9 1.0 Ethanol 1.4 1.4 2.51.4 1.5 — 1,2 Propanediol 4.9 5.0 6.6 4.9 4.0 — Sorbitol — — — — 4.0 —Ethanolamine 0.5 0.8 1.5 0.8 0.1 — TEPAE 0.4 0.4 Protease 0.02 0.0280.04 0.028 0.04 — Lipase — — — — 0.002 — Amylase 0.001 0.002 0.0002 0.01— — PVNO — — Brightener 0.1 0.14 0.15 0.2 0.12 0.12 Silicone antifoam —— — 0.05 — — Mannanase 0.0004 0.0006 — — — — Cellulase 0.0003 0.00020.0003 — — — Amine ethoxylate 0.8 1.3 1.8 2.1 — — polymer AA or MA/AA —— — — 0.6 0.2 DTPMP, DTPA, 0.3 0.3 0.1 — — 0.1 EDTA mixture Microcapsule1 0.5 1.9 0.3 1.2 0.7 0.5 Microcapsule 2 — — 0.5 — 0.2 —

Example #11

The following liquid detergent compositions which provide “softeningthrough the wash” are prepared:

I II III IV V VI LAS 16.0 16.0 16.0 16.0 16.0 16.0 C₂₄EO₇ 2.0 2.0 2.01.2 1.2 1.2 Citric acid 2.5 2.5 2.5 1.5 1.5 1.5 Fatty acid 11.4 11.411.4 6.84 6.84 6.84 Protease 0.48 0.48 0.48 0.35 0.35 0.35 Amylase 0.130.13 0.13 0.08 0.08 0.08 NA Metaborate 1.3 1.3 1.3 0.79 0.79 0.79Chelant 1.5 1.5 1.5 0.9 0.9 0.9 Amine — 0.08 0.08 0.05 — 0.05 Brightener0.14 0.14 0.14 0.09 0.09 0.09 Structurant 0.18 0.18 0.18 0.26 0.26 0.26Ethanol 0.76 0.76 0.76 2.38 2.38 2.38 1,2 Propanediol 8.0 8.0 8.0 4.824.82 4.82 Na Hydroxide 6.2 6.2 6.2 3.8 3.8 3.8 Solvent 2.0 2.0 2.0 1.21.2 1.2 Silicone 0.2 0.2 0.2 0.12 0.12 0.12 Dispersant 0.06 0.06 0.060.04 0.04 0.04 Perfume 0.81 — 0.6 0.48 0.65 0.40 Dye 0.004 0.003 0.0050.003 0.003 — Bentonite clay 3.36 3.36 3.36 3.36 3.36 3.36 Microcapsule1 — 2.0 0.5 0.7 0.3 — Microcapsule 2 — — — 0.3 1.2 0.7

Example #12

The following concentrated liquid detergent formulations are prepared:

I II III IV V VI VII VIII MEA 8.6 8.0 8.0 8.0 8.0 8.0 8.0 8.0Propanediol 19.5 22.0 21.9 21.8 21.0 21.0 22.0 21.9 Sulfite solution0.15 0.15 0.15 0.15 0.15 0.15 — — C₂₄EO₇ 19.6 19.5 19.6 19.4 19.8 19.819.8 19.8 Brightener 0.28 0.38 — 0.28 0.28 0.28 0.28 0.28 LAS 23.7 23.023.1 22.9 23.3 23.3 23.3 23.3 Dispersant 3.2 1.6 1.6 1.6 1.6 1.6 1.6 1.6Fatty acid 17.3 17.3 17.4 17.3 17.6 17.6 17.6 17.6 Perfume 1.5 — 1.5 1.60.9 — 1.5 1.6 Protease 1.16 1.16 1.16 1.16 — — — — Amylase — 0.14 0.140.14 — — — — Mannanase — 0.12 0.12 0.12 — — — — Dye 0.002 0.001 0.0050.005 0.004 0.004 0.001 0.001 Antimicrobial Agent 0.0006 — — — — — — —Preservative: 0.001 — — — — — — — Glutaraldehyde Bentonite clay 0.2 — —— — — — — Structurant 0.2 — — — — — — — Microcapsule 1 2.5 3.5 — 1.1 —2.0 1.7 — Microcapsule 2 — — 2.0 1.2 4.0 2.0 — 3.5

Example #13

The following concentrated/dilute liquid fabric softening compositionsare prepared.

Ingredients 1 2 Softener Active: Rewoquat V3682 17.61 5.2 fromGoldschmidt Silicone: Antifoaming agent: 0.01 0.004 MP10 from DowCorning HEDP (Sodium salt) 0.17 — HCl 0.005 0.013 SRP: Texcare 3639 fromClariant 0.05 — CaCl₂ 0.035 — Stabilizer: PEG-4K Pluriol E4050E 0.50 —Preservative: gluteraldehyde — 0.025 50% - from BASF Perfume — 0.32 Dye0.003 0.0006 Microcapsule 4.0 2.0 Demineralized water Bal. Bal.

Example #14

The following hair conditioners are prepared.

Ingredient 1 2 3 Stearamidopropyldimethyl amine 2.0 1.0 BehenyltrimethylAmmonium Chloride 3.4 Quaternium 18 .75 PEG-2M .5 Emulsifying Wax .5L-glutamic acid .64 Cetyl Alcohol 2.5 .96 2.0 Stearyl Alcohol 4.5 .643.6 Dimethicone/Cyclomethicone 4.2 (15/85 blend) Dimethicone 4.2 4.2Hydroxyethyl Cellulose .25 Glyceryl Monostearate .25 Additional Perfume.3 .2 .2 Chemitech microcapsules .4 .6 Chemitech microcapsules .4 CitricAcid .13 NaOH .014 Benzyl Alcohol .4 .4 .4 EDTA .1 .1 Kathon .0005 .0005.0005 Disodium EDTA .127

Example #15

The following shampoos are prepared:

Example No. Component 1 2 3 4 Water-USP Purified & Q.S. Q.S. Q.S. Q.S.Minors to 100 to 100 to 100 to 100 Ammonium Laureth 10 11.67 10 6Sulfate Ammonium Lauryl 6 2.33 4 10 Sulfate Cocamidopropyl — 2 — —betaine Cocamide MEA — 0.8 0.8 0.8 Citric Acid 0.04 0.04 0.04 0.04Sodium Citrate 0.45 0.45 0.45 0.45 Dihydrate Disodium EDTA 0.1 0.1 0.10.1 Kathon 0.0005 0.0005 0.0005 0.0005 Sodium Benzoate 0.25 0.25 0.250.25 Disodium EDTA 0.1274 0.1274 0.1274 Cetyl Alcohol — 0.6 0.9 0.6Ethylene Glycol 1.5 1.5 1.5 Distearate Polyox PEG7M — — .1 —Trihydroxystearin .25 (Thixin R, Rheox) Polyquaternium-10 0.5 0.15(KG30M) Polyquaternium-10 — — — .25 (LR30M) Guar 0.5 — — Hydroxy-propyltrimonium Chloride1 Dimethicone — 1.4 4.0 (Viscasil 330M)Dimethicone 5.0 microemulsion (Dow 1664) Zinc Pyridinethione 1 Chemitech1 1.5 .5 microcapsules (1) Chemitech .5 .8 microcapsules (2) AdditionalPerfume 0.3 0.7 0.2 0.7 Sodium Chloride 0-3 0-3 0-3 0-3 Ammonium Xylene0-3 0-3 0-3 0-3 Sulfonate

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A microcapsule, which encapsulates a mixture comprising a volatilesubstance, and an additive that has a higher melting point than thevolatile substance and is able to undergo mutual dissolution with thevolatile substance, wherein the mixture exhibits a melting point range,and a portion of, or all of, the melting point range falls within arange from −20 to 60° C.
 2. The microcapsule according to claim 1,wherein the additive is a compound with a melting point within a rangefrom 25 to 200° C.
 3. The microcapsule according to claim 1, wherein theadditive is one or more compounds selected from the group consisting ofalcohols, carboxylic acids, hydroxy acids, and paraffin.
 4. Themicrocapsule according to claim 1, wherein the mixture comprises from 10to 200 parts by weight of the additive per 100 parts by weight of thevolatile substance.
 5. The microcapsule according to claim 1, whereinthe volatile substance is a fragrance.
 6. A method of producing themicrocapsule according to claim 1, comprising: preparing an emulsion ofthe mixture comprising the volatile substance, and the additive that hasa higher melting point than the volatile substance and is able toundergo mutual dissolution with the volatile substance; and adding amembrane material to the emulsion and conducting a polymerization,thereby forming a microcapsule which encapsulates the mixture. 7-16.(canceled)